2,6-C6H3Cl2CHNCH2CH2NMe2 | 145196-03-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,6-C6H3Cl2CHNCH2CH2NMe2
• 英文别名: 2,6-Cl2C6H3CH=NCH2CH2NMe2；2-[(2,6-dichlorophenyl)methylideneamino]-N,N-dimethylethanamine
• CAS: 145196-03-8
• 化学式: C₁₁H₁₄Cl₂N₂
• 分子量: 245.152
• InChiKey: HQZDDAJBWNCDTP-UHFFFAOYSA-N

物化性质

• 沸点：
  318.4±42.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-C6H3Cl2CHNCH2CH2NMe2 以 氘代氯仿 、 甲苯 为溶剂， 生成 PtCl(C₆H₄)(CH₃)2NC₂H₄NCHC₆H₃ClP(C₆H₅)3
  参考文献：
  名称：

  Compound [PtPh₂(SMe₂)₂] as a Versatile Metalating Agent in the Preparation of New Types of [C,N,N‘] Cyclometalated Platinum Compounds

  摘要：

  The reactions of [PtPh2(SMe2)(2)] (1) with ligands RCH=NCH2CH2NMe2 (R = C6H5 (2a), 2-BrC6H4 (2b), 2,6-Cl2C6H3 (2c), 2-ClC6H4 (2d), and C6F5 (2e)) produced compounds [PtPh2{Me2NCH2CH2NCHR}] (3). Compounds 3 led to formation of three different types of [C,N,N'] platinum compounds, including platinum(II) compounds with a seven-membered metallacycle. The reactions of the cyclometalated compounds with triphenylphosphine were also studied.

  DOI：

  10.1021/om030674t

文献信息

• Preparation of Five-Membered Nickelacycles with Anionic C−N−N‘ Terdentate Ligands. X-ray Crystal Structure of [NiCl{2-(CHNCH₂CH₂NMe₂)-3-ClC₆H₃}]
  作者：Rosa M. Ceder、Jaume Granell、Guillermo Muller、Mercè Font-Bardía、Xavier Solans

  DOI：10.1021/om960309k

  日期：1996.10.15

  imines derived from N,N-dimethylethylenediamine, C6RnH5-nCH NCH2CH2NMe2 to [Ni(COD)2]. The molecular structure of [NiCl2-(CHNCH2CH2NMe2)-3-ClC6H3}] has been determined by a single-crystal X-ray crystallographic study. Some ionic compounds [Ni(C−N−N‘)L]BF4 (L = NCMe, heterocyclic amines) were also obtained. The NiC bond of these complexes is inert toward insertion reactions of ethylene or PhC⋮CPh. The action

  五元金属环[Ni（C-N-N'）X]是通过氧化添加衍生自N，N-二甲基乙二胺，C 6 R n H 5 - n CH NCH 2 CH的邻卤代亚胺制备的2 NMe 2至[Ni（COD）2 ]。通过单晶X射线晶体学研究确定了[NiCl 2-（CH NCH 2 CH 2 NMe 2）-3-ClC 6 H 3 }]的分子结构。一些离子化合物[Ni（C-N'N'）L] BF 4（L ＝ NCMe，杂环胺）也被获得。这些配合物的Ni C键对乙烯或PhC⋮CPh的插入反应呈惰性。[Ni（COD）2 ]对二胺C 6 R n H 5 - n CH 2 N（Me）CH 2 CH 2 NMe 2的作用提供了高度不溶的有机镍衍生物，其通过与芳族胺（L）反应TlBF 4的存在导致离子衍生物[Ni（C- N'N '）L] BF 4。使用CuCl 2稳定有机金属Ni（III）化合物因为没有达到氧化剂。配位化合物[NiClBr（N'-N）]，其中N-N'=
• Five- and Seven-Membered Metallacycles in [C,N,N′] and [C,N] Cycloplatinated Compounds
  作者：Raquel Martín、Margarita Crespo、Mercè Font-Bardia、Teresa Calvet

  DOI：10.1021/om800864f

  日期：2009.1.26

  The reactions of cis-[Pt(4-C6H4Me)2(μ-SEt2)]2 with ligands ArCH═NCH2CH2NMe2 (Ar = 4-ClC6H4 (1a); 2-BrC6H4 (1b); 2,6-Cl2C6H3 (1c); C6F5 (1d)) and ArCH═NCH2(4-ClC6H4) (Ar = 4-ClC6H4 (1e); 2-BrC6H4 (1f); 2,6-Cl2C6H3 (1g); C6F5 (1h)) were studied. Several types of compounds were formed including (i) [N,N′] coordination compounds (2a, 2c, 2d), (ii) [C,N,N′] platinum(IV) (3b, 3c), [C,N,N′] platinum(II) (4a)

  的反应中的顺式- [PT（4-C 6 H ^ 4 Me）的2（μ-SET 2）] 2与配体ArCH═NCH 2 CH 2 NME 2（AR = 4-CLC 6 ħ 4（1A）; 2- BRC 6 ħ 4（1B）; 2,6-CL 2 ç 6 ħ 3（1C），C 6 ˚F 5（1D））和ArCH═NCH 2（4-CLC 6 ħ 4）（AR = 4-CLC 6高4（1e）; 2-BrC 6 H 4（1f）; 2,6-Cl 2 C 6 H 3（1g）；研究了C 6 F 5（1h））。形成了几种类型的化合物，包括（i）[N，N']配位化合物（2a，2c，2d），（ii）[C，N，N']铂（IV）（3b，3c），[C，具有五元金属环的N，N']铂（II）（4a）和[C，N]铂（II）（4e）环金属化合物，以及（iii）[C，N，N']铂（II） ）（5c）和具有七元金属环的[C，N]铂（II）（5f，
• Kinetico-Mechanistic Insight into the Platinum-Mediated C−C Coupling of Fluorinated Arenes
  作者：Teresa Calvet、Margarita Crespo、Mercè Font-Bardia、Kerman Gómez、Gabriel González、Manuel Martínez

  DOI：10.1021/om9004934

  日期：2009.9.14

  PtII-metalated compound [PtBr6-(C6F5)(2-C)C5H3CHNCH2(4′-ClC6H4)SEt2] (2c), which contains a five-membered metallacycle with a biaryl linkage involving a C6F5 group. The derivative compounds [PtBr6-(C6F5)(2-C)C5H3CHNCH2(4′-ClC6H4)L] (L = SMe2 (3c), L = PPh3 (4c)) were also prepared, and compound 4c has also been characterized by XRD. The kinetico-mechanistic study of the formation of compound 2c has also

  化合物的反应顺式- [PT（C 6 ˚F 5）2（组2）2 ]与配体亚胺ArCH═NCH 2 CH 2 NME 2（AR = 2- BRC 6 ħ 4（1A）或2,6- CL 2 ç 6 ħ 3（图1b））在甲苯产生配位化合物的顺式- [PT（C 6 ˚F 5）2（ArCH═ ñ CH 2 CH 2 ñ我2）]（2a，2b）含有二齿[N，N']配体。从这一点来看，没有观察到进一步的反应性。化合物2b已经通过单晶XRD表征。在类似条件下，亚胺配体2-BrC 6 H 4 CH = NCH 2（4'-ClC 6 H 4）（1c）生成PT II金属化化合物[PTBr 6-（C 6 F 5）（2- C）C 5 H 3 CH N CH 2（4'-ClC 6 H 4）SEt 2 ]（2c），其中含有带有C 6 F 5基团的联芳基连接的五元金属环。衍生物化合物[PTBr 6-（C 6 F 5）（2- C）C
• Platinum-Mediated C−H Bond Activation of Arene Solvents and Subsequent C−C Bond Formation
  作者：Joan Albert、Ramon Bosque、Margarita Crespo、Jaume Granell、Judit Rodríguez、Javier Zafrilla

  DOI：10.1021/om100743z

  日期：2010.10.25

  The reactions of cis-[PtCl2(SOMe2)(2)] and imines 2,6-Cl2C6H3CH=NCH2(4-XC6H4) (1a, X = H; 1b, X = Cl), 2,6-Cl2C6H3CH=NCH2(2,6-F2C6H3) (1f), and 2,6-Cl2C6H3CH=N(4-ClC6H4) (1g) carried out in toluene at 90 degrees C in the presence of sodium acetate dissolved in methanol produced compounds [PtCl(MeC6H3)(2-ClC6H3)CHNR)}SOMe2] (R = CH2C6H5 (4a), CH2(4-ClC6H4) (4b), CH2(2,6-F2C6H3) (4f), and 4-ClC6H4 (4g)), containing seven-membered platinacycles via "formal insertion" of a toluene molecule in the metallacycle. These compounds are formed in a process involving several steps, the most relevant being intermolecular C-H activation of a solvent toluene molecule and formation of a carbon-carbon bond. The reaction of cis-[PtCl2(SOMe2)(2)] and imine 2,6-Cl2C6H3CH=NCH2(4-CIC6H4) (1b) under analogous conditions was also carried out using other arene solvents such as benzene and ortho-, meta-, and para-xylene and produced in all cases seven-membered platinacycles. DFT calculations indicate that the stability of the metallacycles increases in the order p-xylyl < m-xylyl < o-xylyl < tolyl < phenyl and have helped to suggest a possible reaction path.
• Competition between intramolecular oxidative addition and ortho metalation in organoplatinum(II) compounds: activation of aryl-halogen bonds
  作者：Craig M. Anderson、Margarita Crespo、Michael C. Jennings、Alan J. Lough、George Ferguson、Richard J. Puddephatt

  DOI：10.1021/om00054a031

  日期：1991.8

  The ligands 2-XC6H4CH = NCH2CH2NMe2 (1) react with [Pt2Me4(mu-SMe2)2] (2) to give [PtMe2(2-XC6H4CH = NCH2CH2NMe2)] (3), which then react either by ortho metalation to give CH4 and [PtMe-(2-XC6H3CH = NCH2CH2NMe2)] (4) or undergo oxidative addition of the C-X bond to give [PtXMe2-(C6H4CH = NCH2CH2NMe2)] (5). These complexes, and related compounds with modified aryl substituents, have been characterized by NMR spectroscopy, and the derivative [PtClMe2(ClC6H3CH = NCH2CH2NMe2)] (7b) has been characterized crystallographically. The complex [PtMe(C6H4CH = NCH2CH2NMe2)] reacts with CD3Br or MeI to give [PtBrMe(CD3)(C6H4CH = NCH2CH2NMe2)] or [PtIMe2(C6H4CH = NCH2CH2NMe2)], respectively, initially by trans oxidative addition. The ligands 2-XC6H4CH = NR (R = Ph, Pr) react with [Pt2Me4(mu-SMe2)2] to give similar products of ortho metalation, [PtMe(2-XC6H3CH = NR)(SMe2)], or oxidative addition, [PtXMe2(C6H4CH = NR)(SMe2)]. The kinetics of the reaction of 3 to give 4 or 5 have been studied, and the reactions each follow first-order kinetics. The activation parameters for both types of reaction are similar, and since the ortho metalation is presumed to occur by concerted C-H oxidative addition followed by rapid reductive elimination of methane, it is suggested that the oxidative addition of aryl-bromide or aryl-chloride bonds also occurs by a concerted mechanism. The rates of reaction are C-Br > C-Cl > C-H, and internal competition reactions give the sequence C-Cl > C-H > C-F. Hence, the overall reactivity series is C-Br > C-Cl > C-H > C-F, the series of increasing C-X bond energies. These are the first examples of aryl-halogen bond activation by platinum(II) complexes.